Fukuyama Group - Group Meeting Problems

01/08/2003

1
O O O
SOCl2 (ex.)
Ph NO2 Ph Ph
N N N
H rt, 52% H H
N N
O O

2
O O
O NHMe 80~110 °C, 5 h EtO2C
O NMe
Ph OEt 74% Ph
O O O

3
H H
N BrCN, Et2O, 0 °C; N
NH2 NHAc
AcCl, Et3N diphenyl ether
190 °C, 2.5 h N
55%
76%

4 SMe 1) I2, THF, 69%

2) Na2CO3
O NEt THF/dioxane/H2O, reflux, 71%

3) 0.5 N NaOH NHEt

EtOH/H2O, reflux, 64% OH
(racemic)

5 O

1) KOt-Bu, O2, P(OEt)3 H

HOt-Bu, DME, 79% O
N N
2) NaBH4, THF, 76%
H
N 3) NaIO4, 53%
N
PhO2S PhO2S
 Fukuyama Group - Group Meeting Problems
01/15/2003

1
OH
O 1) LDA, THF, –78 °C
O 2) CF3SO3Me, CH2Cl2, 0 °C to rt

3) t-BuOK, THF
O

2
OH (NH4)2SO3·H2O NH2
OH OH
NH3·H2O
200 °C, 5 d
91%

3 1) n-Bu3P, DMF, 0 °C
H
H
N
N O O
S S then O O

47% Br Br
N N 2) 1,2,2,6,6-pentamethyl-
H H N N
piperidine (cat) H H
toluene, reflux, 72%

Me O MeCO2Me
O t-BuNC, DMAD CO2Me
O O
CH2Cl2, rt, 24 h
O 94% O NHt-Bu

5
O CO2Et

SnCl2 (5 eq)
S
S S EtOH S
reflux, 2 h N
NO2 H
98%
 Fukuyama Group - Group Meeting Problems
01/22/2003

1
n-BuLi (1 eq), THF;
B(n-Bu)3 (1.1 eq); Ph
Ph BCl3 (1.1 eq);
OH
OMOM MeOH;
n-Bu
30% aq. H2O2-NaOH
89%

2
CO (2-3 bar), Pd(PPh3)4
K2CO3, n-Bu4NBr O
I
O

NHTs
CH3CN N
Ts
70-80 °C
61%

O
NH4Cl
3 CO2Me toluene
MeO2C N
rt, 1 hr;
+ OHC C6H13
O O
NH2 CN
N
O N C6H13
Ph
reflux, 1.5 hr

4
SO2Ph O
1) t-BuOLi, –60 °C
2) DDQ O
O + O
3) toluene, reflux
O O
O

O
5 OTIPS

1) PhI(CN)OTf 2) KF on Al2O3
SnBu3 CH2Cl2, –40 °C; (under air)
MeO MeO
LHMDS N
DME, –40 °C
MeO NHTs MeO